Seed oil compositions

ABSTRACT

The present invention is directed to seed oil compositions that can be used for cooking and frying applications. These oil compositions of the present invention have advantageous stability characteristics. In some embodiments, the oil compositions have a low concentration of α-linolenic acid.

REFERENCE TO RELATED APPLICATONS

This application claims the benefit under 35 USC 119(e) from U.S.provisional application Ser. No. 60/633,914 filed Dec. 6, 2004, and Ser.No. 60/625,506 filed Nov. 4, 2004.

BACKGROUND

The present invention relates to non-hydrogenated or partiallyhydrogenated non-animal oils having a low level of trans-fatty acids andimproved flavor and performance attributes especially suitable for foodapplications and processes for the preparation thereof.

As consumers have become more aware of the health impact of lipidnutrition, consumption of oils with high levels of unsaturated andpolyunsaturated fats and low levels of trans-fats is desirable.

Many oils are chemically hydrogenated; hydrogenation is used to improveperformance attributes such as stability. When an oil is hydrogenated,the number of olefinic unsaturations in the fatty acids is reduced.However, hydrogenation can affect the stereochemistry of double bonds byeither moving the double bond to another position in the fatty acid orcausing the primarily cis-double bonds to isomerize to trans-doublebonds. Isomerization of cis-fatty acids to trans-fatty acids isundesirable due to the negative health issues relating to theconsumption of trans-fatty acids.

One application of oils is for use during deep-frying. The temperaturesof deep-frying can cause the oil to oxidize and thus, degrade fasterthan it would at a lower temperature. Thus, many unhydrogenated oilswith high levels of unsaturated or polyunsaturated fats have limited usein deep-frying operations due to their instability; deep-frying is animportant segment of the food processing industry. Many non-hydrogenatedsoybean oils are unstable and easily oxidized during cooking, which inturn creates off-flavors of the oil and compromises the sensorycharacteristics of foods cooked in such oils.

Generally, oils extracted from soybeans have an α-linolenic acid (ALA)content of 5%-10%. There are several factors that affect oxidativestability and flavor stability. The amount of ALA in the oil is one ofthese factors because it is known to oxidize faster than other fattyacids with fewer double bonds. In addition, ALA has been suggested as aprecursor to undesirable odor and flavor development in foods. Thus, anoil having a low ALA content and an improved stability in its flavor andperformance attributes for use in food operations is needed. Oils of thepresent invention meet these needs.

SUMMARY OF THE INVENTION

One embodiment of the invention is directed to an unhydrogenated plantoil composition comprising linoleic acid or a derivative thereof, andless than about 3 wt. % α-linolenic acid or a derivative thereof, basedupon the total weight of fatty acids or derivatives thereof in thecomposition, the composition having an anisidine value of less than 2.0,and being derived from a non-algal oil.

Additional embodiments of the invention are directed to a soy oilcomposition comprising linoleic acid or a derivative thereof, and lessthan about 3 wt. % α-linolenic acid or a derivative thereof, based uponthe total weight of fatty acids or derivatives thereof in thecomposition, the composition having either: an anisidine value of lessthan 2.0; a peroxide value of less than 0.3 meq/kg when the compositionis free of added stabilizers; less than 1 wt. % trans-fatty acid; or notmore than about 80 wt. % oleic acid or a derivative thereof, and atleast 800 ppm tocopherols.

Another embodiment of the invention is directed to a crude soy oilcomposition comprising linoleic acid or a derivative thereof and lessthan about 3 wt. % α-linolenic acid or a derivative thereof, based uponthe total weight of fatty acids or derivatives thereof in thecomposition, the composition having a peroxide value of 0 meq/kg.

Yet another embodiment of the invention is directed to a soy oilcomposition comprising less than 56.0 wt. % linoleic acid or aderivative thereof and less than about 3 wt. % α-linolenic acid or aderivative thereof, based upon the total weight of fatty acids orderivatives thereof in the composition.

Another embodiment of the invention is directed to a soy oil compositioncomprising from about 55 to about 85 wt. % oleic acid or a derivativethereof, from about 2 to about 35 wt. % linoleic acid or a derivativethereof, and not more than about 8 wt. % α-linolenic acid or aderivative, based upon the total weight of fatty acids or derivativesthereof in the composition.

Yet another embodiment of the invention is directed to a soy oilcomposition comprising from about 25 to about 85 wt. % oleic acid or aderivative thereof, from about 2 to about 65 wt. % linoleic acid or aderivative thereof, not more than about 8 wt. % α-linolenic acid or aderivative thereof, and not more than about 10 wt. % saturated fattyacid or a derivative thereof, based upon the total weight of fatty acidsor derivatives thereof in the composition.

Yet another embodiment of the invention is directed to a soy oilcomposition comprising from about 20 to about 30 wt. % stearic acid or aderivative thereof, not more than about 40 wt. % linoleic acid or aderivative thereof, not more than about 30 wt. % oleic acid or aderivative thereof, not more than about 8 wt. % α-linolenic acid or aderivative thereof, and not more than about 10 wt. % palmitic acid or aderivative thereof, based upon the total weight of fatty acids orderivatives thereof in the composition.

Yet another aspect of the invention is directed to a process formaintaining the storage stability of an oil during shipment or storage,the process comprising storing an oil of the invention in a container ata temperature ranging from about 4 to about 45° C. for at least onemonth, wherein the oil has an anisidine value of less than 3 afterstorage.

Yet another aspect of the invention is directed to a process formaintaining the storage stability of an oil during shipment or storage,the process comprising storing an oil of the invention in a container ata temperature ranging from about 4 to about 45° C. for at least onemonth, wherein the absolute change in the anisidine value of the oilduring storage is no more than about 20.

Yet another aspect of the invention is directed to a process formaintaining the storage stability of an oil during shipment or storage,the process comprising storing an oil of the invention in a container;and freezing the container.

Yet another aspect of the invention is directed to a process formaintaining the storage stability of an oil during shipment or storage,the process comprising encapsulating the oil of the invention in anencapsulation material.

Yet another aspect of the invention is directed to a food composition,beverage, nutritional supplement, or cooking oil comprising an oil ofthe invention.

Yet another aspect of the invention is directed to a method of making afood composition by frying a food product or food analog in an oil ofthe invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of the oil odor intensity versus the amount of timethe oil had been used for frying; the method is described in Example 1.

FIG. 2 is a graph of the oil off odor versus the amount of time the oilhad been used for frying; the method is described in Example 1.

FIG. 3 is a graph of the overall chip acceptability versus the amount oftime the oil had been used for frying; the method is described inExample 1.

DETAILED DESCRIPTION

The oils of the present invention have improved stability in terms oftaste and smell and low levels of trans-fatty acids. In one embodiment,oils of the present invention can be used for deep-frying of foods.Deep-frying requires high temperatures that increase the oxidativestress of an oil. Typically, oils used for deep-frying applications arehydrogenated to decrease the number of double bonds in the oil's fattyacids, which increases the stability of the oil. However, hydrogenationof oils increases the concentration of undesirable trans-fatty acids.Therefore, certain oil compositions of the present invention having atrans-fatty acid concentration less than about 1 wt. % based on thetotal weight of fatty acids in the composition and improved stabilityare advantageous.

Among the various aspects of the present invention is an unhydrogenatedplant oil composition comprising linoleic acid or a derivative thereof,and less than about 3 wt. % α-linolenic acid or a derivative thereof,based upon the total weight of fatty acids or derivatives thereof in thecomposition, the composition having an anisidine value of less thanabout 2.0, and being derived from a non-algal oil.

In another embodiment, a soy oil composition comprising linoleic acid ora derivative thereof, and less than about 3 wt. % α-linolenic acid or aderivative thereof based on the total weight of fatty acids orderivatives thereof in the composition, the composition having aperoxide value less than about 0.3 meq/kg when the composition iswithout added stabilizers. In another embodiment, a soy oil compositioncomprising linoleic acid or a derivative thereof, and less than about 3wt. % α-linolenic acid or a derivative thereof based on the total weightof fatty acids or derivatives thereof in the composition, thecomposition having an anisidine value less than about 2.0.

The process for preparing the oils of the present invention has beendeveloped by optimizing the many factors that affect the rate of theoxidation processes including seed storage and treatment, theconcentrations of pro-oxidants (e.g., oxygen, chlorophyll and metals),the temperature of the system, the exposure of the seed meats or oil tolight and the concentration of stabilizers or antioxidants presentnaturally or otherwise. The relationships between these factors arecomplex. The process improvements of the present invention provide oilcompositions with improved seed oil stability as characterized bysensory and flavor data when compared to seed oils prepared byconventional methods.

I. Oil Compositions

This section describes the oil compositions in terms of the oxidativestability and the fatty acid content of each composition.

A. Oxidative Stability of Oil Compositions

The various oil compositions of the invention are oils extracted fromvarious non-animal sources. Advantageously, the compositions of theinvention possess greater stability than known oil compositions.

Generally, the stability of oils is important for determining their use.For example, oils with low concentrations of unsaturated fatty acidsusually resulting from partial hydrogenation are used for deep-fryingapplications. Typically, these oils are partially hydrogenated due tothe lower stability of unsaturated fats to oxidative instability, whichcan result from high deep-frying temperatures. However, hydrogenation ofoils results in the formation of trans-fatty acids, which are known tonegatively impact cardiovascular health. Thus, there is interest inpreparing stable oils wherein the trans-fatty acid content is low foruse in deep-frying applications, and several of the oil compositions ofthe invention are suitable for such use.

Generally, oils having a greater number of olefinic functionalities havehigher oxidation rates than oils having a lower number of olefinicfunctionalities. The reaction schemes describing the oxidation ofunsaturated fatty acids (UFAs) include radical chain reactionscharacterized as initiation, propagation and termination reactions. Anexample of an initiation reaction involves abstracting a hydrogen atomfrom a fatty acid to produce a fatty acid with a free radical. UFAshaving more than one double bond and having an allylic carbon are morereactive than polyunsaturated fatty acids having other configurationsbecause the allylic hydrogen is more easily abstracted and the allylicradical is more stable than other radicals. During propagation, the UFAwith an allylic radical can react with molecular oxygen to produce aperoxide compound. The peroxide compound can react with another UFA toabstract a hydrogen atom and produce another fatty acid radical in apropagation step. Alternately, an allylic radical can react with anotherradical to produce an inactive product in a termination step.

Factors affecting the oxidation of oils with one or more unsaturatedfatty acids are a function of the concentration of agents which initiatethe abstraction of a hydrogen atom from a UFA, the concentration ofmolecular oxygen, the concentration of compounds which react with theradicals to form stable products (e.g., stabilizers or other radicalsthat result in termination) and various other reaction conditions thatincrease or decrease the reaction rates of the oxidation reactions.Molecular oxygen is one of the most important species needed to sustainthe production of peroxide compounds from UFAs and the factors discussedherein above have complex relationships.

Generally, the relationship of the concentration of pro-oxidants, whichinitiate the formation of radical species, to the stability of thehighly unsaturated oils depends on the specific pro-oxidant and theinitiation reaction that occurs. When molecular oxygen is taken up in apropagation step of the overall oxidation reaction scheme, therelationship between molecular oxygen concentration and the rate of UFAoxidation is approximately linear. However, molecular oxygen canparticipate in other types of reactions in the overall oxidationreaction scheme. For example, a proposed initiation mechanism is theabstraction of hydrogen from an UFA by trace metal ions. Furthermore, ithas been found that UV light and temperature increase the rates ofdirect attack by oxygen on UFAs. It is also believed that UFAs areoxidized by hydrogen peroxide produced from metal-catalyzed waterdecomposition or by reaction with trace amounts of singlet oxygen. Allof these reactions are plausible and lead to complex relationshipsbetween the processing factors, stability, and oil quality discussedherein below.

While the relationship of the concentration of stabilizers to the rateof UFA oxidation depends on the specific stabilizer, this relationshipcan be complicated by the presence of more than one stabilizer. Theaddition of multiple stabilizers can act to stabilize each other andwhen this occurs, a combination of two or more stabilizers can be moreeffective at terminating free radicals than a single stabilizer.

Despite the complexity of UFA oxidation, the stability of compositionscontaining UFAs can be determined by measuring certain types ofcompounds produced by the various oxidation reactions. For example, theperoxide value (PV) is the concentration of peroxide compounds in theoil measured in meq/kg. Peroxide compounds are produced during UFAoxidation, thus, the higher the value of PV, the more UFA oxidation thathas occurred. Furthermore, the PV of the oil can be minimized byreducing the formation of peroxides or by removing/decomposing theperoxides or hydroperoxides present in the oil. The PV can be minimizedby a variety of techniques, including, but not limited to processingprotocols.

Another type of measurement that is utilized to assess thepost-oxidative stress that the oil has been exposed to is referred to asthe anisidine value (AV) of the oil. The AV indicates the amount ofoxidation that the oil has experienced prior to measurement and is ameasure of the concentration of the secondary oxidation products. The AVof an oil is a measure of the amount of non-volatile aldehydes and/orketones in the oil. As the AV of the oil measures the non-volatilealdehyde and/or ketone concentration in the oil (typically, unitless),it is a measure of its oxidative history. Aldehydes and ketones areproduced from the decomposition of the peroxide or hydroperoxidespecies, which are primary oxidation products of the olefinicfunctionality on a fatty acid. Methods for measuring PV or AV of an oilare well known in the art and include AOCS Cd 8-53 and AOCS Cd 18-90,respectively.

Minimizing the amount of oxidation measured by PV and AV can havesignificant implications when assessing the oxidative stability of anoil. For example, peroxides and hydroperoxides can readily decompose toform off flavors and aldehydes and ketones, which can act as catalystsfor the further oxidative decomposition of the oil.

A method for determining the oxidative stability is the oxidativestability index (OSI); one method for measuring OSI is AOCS Cd 12b-92.The value for the OSI is the time (usually in hours) before the maximumrate change of oxidation (generally referred to as the propagation phaseof the oxidation reaction); this time is usually called the inductionperiod. Although there are many factors that affect an oil's OSI value,the value is useful along with the other measures for makingsemi-quantitative predictions about oil stability.

Another method for determining the oxidative stability of an oil, is toutilize a standardized sensory evaluation. Generally, the standardizedsensory evaluation assesses the smell, taste, tactile attributes andflavor of the oil and also, the characteristics of a food productcontaining the oil by deep-frying the food in the oil or otherwiseincorporating the oil in the food. For example, many characteristics ofthe oil and foods prepared using the oils or having the oil as aningredient can be evaluated. In addition, the trained panelists canselect from a variety of numeric scales to rate the acceptability of theoils tested in the sensory evaluation. A person skilled in the art wouldbe able to design an appropriate sensory evaluation. The sensoryevaluation results determine the acceptability of the oil for thespecific use and as such, are an important measure of oil stability.

Specific odor and taste indicators associated with oils include bacony,beany, bitter, bland, burnt, buttery, cardboardy, corny, deep fried,fishy, fruity, grassy, green, hay, heated oil, hully, hydrogenated oil,lard, light struck oil, melon, metallic, musty, nutty, overheated oil,oxidized, pointy, paraffin oil, peanut oil, pecan oil, petroleum,phenolic, pine oil, petroleum, phenolic, pine oil, plastic, pondy,pumpkin, rancid, raw, reverted oil, rubbery, soapy, sour, sulfur,sunflower seed shell, watermelon, waxy, weedy and woody. Typically, oilscontaining more than four double bonds are characterized by a fishy orpondy odor. One embodiment of the present invention is to produce oilscontaining more than four double bonds, which are bland or buttery intaste and odor at the time of manufacture. Another embodiment of theinvention is to have these oils retain their bland or buttery sensoryproperties when stored for several months.

B. Low α-Linolenic Acid (ALA) Plant Oil Compositions

As discussed herein above, oils having a low content of saturated fattyacids and a high stability are useful for deep-frying or other hightemperature applications. The process of the present invention can beused to prepare an unhydrogenated plant oil composition comprisinglinoleic acid or a derivative thereof, less than about 3 wt. %α-linolenic acid or a derivative thereof, based upon the total weight offatty acids or derivatives thereof in the composition, the compositionhas an anisidine value of less than about 2.0, wherein the compositionis derived from a non-algal oil. In another embodiment, the oilcomposition is derived from almond, avocado, babassu, borage,blackcurrant seed, canola, castor bean, coconut, corn, cottonseed,Echium, evening primrose, flax seed, gooseberry, grapeseed, groundnut,hazelnut, linseed, mustard, olive, palm, palm kernel, peanut, perilla,pine seed, poppy seed, pumpkin seed, rapeseed, redcurrant, rice bran,safflower, sesame seed, soybean, sunflower, tea, walnut, or wheat germoil. In a further embodiment, the oil composition is derived from an oilother than a marine oil.

In a further embodiment, a soy oil composition comprises less than 5,10, 15, 20, 25, 30, 35, 40, 45, 50, 51, 52, 53, 54, 55 or 56 wt. %linoleic acid or a derivative thereof, based on the total weight offatty acids or derivatives thereof in the composition.

In another embodiment, a soy oil composition comprises linoleic acid ora derivative thereof, and less than about 3 wt. % α-linolenic acid or aderivative thereof, based upon the total weight of fatty acids orderivatives thereof in the composition, the composition having ananisidine value of less than about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7,0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2.0.

In another embodiment, a soy oil composition comprises linoleic acid ora derivative thereof and less than about 3 wt. % α-linolenic acid or aderivative thereof, based upon the total weight of fatty acids orderivatives thereof in the composition, the composition having aperoxide value of less than 0.1, 0.2, or 0.3 meq/kg when the compositionis free of added stabilizers.

In yet another embodiment, a soy oil composition comprises linoleic acidor a derivative thereof, less than 1 wt. % trans-fatty acid, and lessthan about 3 wt. % α-linolenic acid or a derivative thereof, based uponthe total weight of fatty acids or derivatives thereof in thecomposition.

In one embodiment, a crude soy oil composition comprises linoleic acidor a derivative thereof and less than about 3 wt. % α-linolenic acid ora derivative thereof, based upon the total weight of fatty acids orderivatives thereof in the composition, the composition having aperoxide value of 0 meq/kg.

In another embodiment, a soy oil composition comprises linoleic acid ora derivative thereof, not more than about 80 wt. % oleic acid or aderivative thereof, and less than about 3 wt. % α-linolenic acid or aderivative thereof, based upon the total weight of fatty acids orderivatives thereof in the composition, and at least 800 ppmtocopherols.

In another embodiment, the unhydrogenated plant oil compositioncomprises less than about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60,65, 70, 75 or 80 wt. % oleic acid or a derivative thereof, based on thetotal weight of fatty acids or derivatives thereof in the composition.In another embodiment, the unhydrogenated plant oil comprises at least850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400,1450, 1500, 1550, 1600, 1650, 1700, 1750, 1800, 1850, 1900, 1950, 2000,2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200,3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400,4500, 4600, 4700, 4800, 4900, or 5000 ppm tocopherols or more. Inanother embodiment, the unhydrogenated plant oil comprises less thanabout 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3,1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7,2.8, 2.9 or 3 wt. % α-linolenic acid or a derivative thereof, based uponthe total weight of fatty acids or derivatives thereof in thecomposition. In another embodiment, the composition has an anisidinevalue of less than about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9,1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2.0.

In one embodiment, the soy oil compositions have an ALA (C18:3n3)content of up to about 3 wt. % based on the total weight of fatty acidsin the composition. Preferably, the seeds extracted contain a similarproportion of ALA to total fatty acid content as the oil composition.Therefore, the ALA content in the whole seed is up to about 3.4 wt. %based on the total weight of fatty acids in the composition.Furthermore, the ALA content in the oil throughout process is less thanabout 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3,1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8,2.9 or 3 wt. % based on the total weight of fatty acids in thecomposition. In a particular embodiment, the ALA content in the oil isup to about 1.5, 1.6, 1.8, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7 or 2.8wt. % based on the total weight of fatty acids in the composition; or upto about 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4 or 2.5 wt. %based on the total weight of fatty acids in the composition. Preferably,the ALA content of the oil composition is from about 2.0 wt. % to about3.0 wt. % based on the total weight of fatty acids in the composition;from about 2.2 wt. % to about 3.0 wt. % based on the total weight offatty acids in the composition; from about 2.2 wt. % to about 2.8 wt. %based on the total weight of fatty acids in the composition; or fromabout 2.6 wt. % to about 2.8 wt. % based on the total weight of fattyacids in the composition.

In another embodiment, the whole soybean or soy oil has a linoleic acid(LA, C18:2n6) content of at least about 5, 10, 15, 20, 25, 30, 35, 40,45, 50, or 55 wt. % based on the total weight of fatty acids in thecomposition. Furthermore, the whole soybean or soy oil has an ALAcontent of up to about 1.5 wt. % and a LA content of at least about 35,40, 45, 50, 51, 52, 53, 54, or 55 wt. % based on the total weight offatty acids in the composition; an ALA content of up to about 1.8 wt. %and a LA content of at least about 35, 40, 45, 50, 51, 52, 53, 54, or 55wt. % based on the total weight of fatty acids in the composition; anALA content of up to about 2 wt. % and a LA content of at least about35, 40, 45, 50, 51, 52, 53, 54, or 55 wt. % based on the total weight offatty acids in the composition; an ALA content of up to about 2.2 wt. %and a LA content of at least about 35, 40, 45, 50, 51, 52, 53, 54, or 55wt. % based on the total weight of fatty acids in the composition; or anALA content of up to about 2.5 wt. % and a LA content of at least about35, 40, 45, 50, 51, 52, 53, 54, or 55 wt. % based on the total weight offatty acids in the composition.

In yet another embodiment, the whole soybean or soy oil compositionduring or after processing has an ALA content of up to about 2.5 wt. %based on the total weight of fatty acids in the composition and atocopherol (e.g., α-tocopherol, β-tocopherol, γ-tocopherol) content ofat least about 400, 450, 500, 600, 700, 800, 805, 810, 820, 830, 840,850, 860, 870, 880, 890, 900, 1000, 1100, 1200, 1300, 1400, 1500, or1600 ppm or more.

In a further embodiment, the whole soybean or soy oil composition duringor after processing has an ALA content of up to about 2.5 wt. % based onthe total weight of fatty acids in the composition and a PV during orafter processing of up to about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.9or 1. In a particular embodiment, the crude oil has an ALA content of upto about 2.5 wt. % based on the total weight of fatty acids in thecomposition and a PV during or after processing of up to about 0.1, 0.2,0.3, 0.4 or 0.5.

Alternately, the whole soybean or soy oil composition during or afterprocessing has an ALA content of up to about 2.5 wt. % based on thetotal weight of fatty acids in the composition and an AV during or afterprocessing of up to about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9,1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2. In a particularembodiment, the refined, bleached and deodorized (RBD) oil compositionhas an ALA content of up to about 2.5 wt. % based on the total weight offatty acids in the composition and an AV of up to about 0.1, 0.2, 0.3,0.4 or 0.5.

In yet a further embodiment, the soy RBD oil has an ALA content of up toabout 2.5 wt. % based on the total weight of fatty acids in thecomposition and an OSI of at least about 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5,9, 9.5 or 10 wherein the oil is not hydrogenated and does not have addedstabilizers.

Any of the oil compositions of section 1.C. has a frying life at least25% longer as compared to that of an oil composition comprising about8-10 wt. % α-linolenic acid or a derivative thereof and otherwise havingthe same composition except that linoleic acid content is decreased bythe same amount as α-linolenic acid content is increased.

In one embodiment, an oil composition having an ALA content of less thanabout 3 wt. % based on a total weight of fatty acids in the compositionis used for deep-frying wherein the food which is deep-fried has asignificantly better flavor quality relative to that of food fried in anoil composition having an ALA content of about 5 to about 10 wt. % basedon a total weight of fatty acids in the composition, wherein the flavorquality is determined by a standardized sensory evaluation. In anotherembodiment, an oil composition having an ALA content of less than about3 wt. % based on a total weight of fatty acids in the composition has asignificantly reduced overall room-odor intensity relative to theoverall room-odor intensity of an oil having an ALA content of about 5to about 10 wt. % based on a total weight of fatty acids in thecomposition, wherein the room-odor intensity is determined by astandardized sensory evaluation.

Further, any one of the oil composition embodiments described in sectionI.C. can be derived from an oil other than a marine oil, such as a fishoil or an algal oil. Further, the composition of the oils describedabove can be derived from a plant oil other than blackcurrant oil,borage oil, Echium oil, evening primrose oil, gooseberry oil, hemp oil,or redcurrant oil.

Any one of the oil composition embodiments described in section I.C. canbe derived from a genetically-modified seed selected from the groupconsisting of Arabidopsis, canola, carrot, coconut, corn, cotton, flax,linseed, maize, palm kernel, peanut, potato, rapeseed, safflower,soybean, sunflower, tobacco, and mixtures thereof.

The present invention is also useful for extracting and purifyingpolyunsaturated fatty acids low in alpha-linolenic acid from planttissue, including plant seed tissue. For example, the methods of theinvention are useful for the extraction and/or stabilization ofpolyunsaturated fatty acids low in alpha-linolenic acid from recombinantplants (such as Glycine max (soybean), Helianthus annuus (sunflower),Sinapis alba, Brassica spp. (including B. napus, B. rapa, B. juncea))produced with, for example, the compositions and methods of U.S. Pat.Nos. 6,680,396; 6,583,303; 6,559,325; 6,441,278; 6,407,317; 6,323,392;6,303,849; 6,270,828; 6,201,145; 6,169,190; 6,133,509; 6,084,157;6,063,947; 5,969,169; 5,965,755; 5,859,350; 5,850,030; 5,850,026;5,767,338; 5,763,745; 5,750,827; 5,714,670; 5,714,669; 5,714,668;5,710,369; 5,710,366; 5,638,637; 5,625,130; 5,557,037; 5,534,425;5,530,183; 5,387,758; and also U.S. patent application Ser. Nos.20040098762; 20040049813; 20040010819; 20040006792; 20030172399;20030163844; 20030159176; 20030154514; 20030079250; 20030066105;20020129408; 20020092042; and 20020042935 (the prior references areherein incorporated by reference).

Soybean germplasms with a low content of linolenic acid have beendeveloped (See e.g. Takagi et al., Agric. Biol. Chem. (1990) 54,1735-1738; Fehr et al., Crop Sci. (1992) 32,903-906; Rahman and Takagi,Theor. Appl. Genet. (1997) 94, 299-302; Rahman et al., Crop Sci. (1998)38, 702-706; Rahman et al., Crop Science (2001) 41, 26-29). Inheritancestudies showed that low linolenic acid is controlled by either a singlelocus or two loci. The single locus fan was found in C1640 (Wilcox andCavins, Theor. Appl. Genet. (1985) 71, 74-78); PI 361088B (Rennie etal., Crop Sci. (1988) 28, 655-657); PI 123440 (Rennie and Tanner,Soybean Genet. Newsl. (1989) 16, 25-26); A5 (Rennie and Tanner, CropSci. (1991) 31, 297-301); and M-5 (Rahman et al., Breed. Sci. (1996) 46,155-158). Fan2 was found in A23 (Fehr et al., Crop Sci. (1992) 32,903-906); fanx in KL-8 (Rahman and Takagi, Theor. Appl. Genet. (1997)94, 299-302); and fanxa in M-24 (Rahman et al., Crop Sci. (1998) 38,702-706). Evidence of two loci were found in A16 and A17 (fanfan2, Fehret al., Crop Sci. (1992) 32, 903-906); MOLL (fanfanx, Rahman and Takagi,Theor. Appl. Genet. (1997) 94, 299-302); and LOLL (fanfanxa, Rahman etal., Crop Sci. (1998) 38, 702-706). The germplasms A16, A17, and LOLLare reported to contain 250 to 280 g kg-1 linolenic acid, which is muchlower than normally occurs in soybean oil. The methods and compositionsof the invention are useful in the extraction and/or stabilization ofpolyunsaturated fatty acids from soybean produced according to the abovelisted reports.

Many breeding studies have been conducted to improve the fatty acidprofile of Brassica varieties. Pleines and Friedt (Fat Sci. Technol.(1988) 90(5), 167-171) describe plant lines with reduced C18:3 levels(2.5-5.8%) combined with high oleic content (73-79%). Rape producingseed oil with 3% linolenic acid and 28% linoleic acid is disclosed inScarth et al., Can. J. Plant Sci (1988) 68, 509-511. Roy and Tarr (Z.Pflanzenzuchtg, (1985) 95(3), 201-209) teach transfer of genes throughan interspecific cross from Brassica juncea into Brassica napusresulting in a reconstituted lien combining high linoleic with lowlinolenic acid content. Roy and Tarr (Plant Breeding (1987) 98, 89-96)discuss development of B. napus having improved linolenic and linolenicacid content. EPO Application No.323,751, published Jul. 12, 1989,discloses seeds and oils having greater than 79% oleic acid combinedwith less than 3.5% linolenic acid. The methods and compositions of theinvention are useful in the extraction and/or stabilization ofpolyunsaturated fatty acids from Brassica produced according to theabove listed reports.

C. Low, Mid and High Oleic Acid Soy Oil Compositions

It is sometimes desirable for a soy oil to include more oleic acid thanis present in conventional soy oil to provide an oil that is heat andoxidation stable at deep-frying temperatures without the need forhydrogenation. In one embodiment of the invention, a soy oil compositioncomprises from about 55 to about 85 wt. % oleic acid or a derivativethereof, from about 2 to about 35 wt. % linoleic acid or a derivativethereof, and not more than about 1, 2, 3, 4, 5, 6, 7 or 8 wt. %α-linolenic acid or a derivative thereof, based upon the total weight offatty acids or derivatives thereof in the composition. In anotherembodiment, not more than about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8,0.9, 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0 or 8.0 wt. % α-linolenic acid ora derivative thereof is present in the soy oil composition. In apreferred embodiment, not more than about 4 wt. % α-linolenic acid or aderivative thereof, and less than 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 wt. %saturated fatty acid or a derivative thereof is present in the soy oilcomposition.

In another embodiment, a soy oil composition comprises from about 25 toabout 85 wt. % oleic acid or a derivative thereof, from about 2 to about65 wt. % linoleic acid or a derivative thereof, not more than about 1 2,3, 4, 5, 6, 7 or 8 wt. % α-linolenic acid or a derivative thereof, andnot more than about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 wt. % saturatedfatty acid or a derivative thereof, based upon the total weight of fattyacids or derivatives thereof in the composition. In a preferredembodiment, not more than about 4 wt. % α-linolenic acid or a derivativethereof is present in the composition.

D. High Stearic Acid Soy Oil Compositions

In some applications, it is desirable for a soy oil to include arelatively high stearic acid (C18:0) content as compared to conventionalsoy oils, which contain about 5 wt. % stearic acid. In one embodiment ofthe invention, a soy oil composition comprises from about 20 to about 30wt. % stearic acid or a derivative thereof, less than about 5, 10, 15,20, 25, 30, 35 or 40 wt. % linoleic acid or a derivative thereof, lessthan about 5, 10, 15, 20, 25 or 30 wt. % oleic acid or a derivativethereof, not more than about 8 wt. % α-linolenic acid or a derivativethereof, and less than about 10 wt. % palmitic acid or a derivativethereof, based upon the total weight of fatty acids or derivativesthereof in the composition. In one embodiment, the composition containsabout 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 wt. % palmitic acid or aderivative thereof. In another embodiment, the composition containsabout 1, 2, 3, 4, 5, 6, 7 or 8 wt. % α-linolenic acid or a derivativethereof.

For any one of the preceding oil compositions described above except forthose that are specifically unhydrogenated, the compositions can bepartially hydrogenated or transesterified. Preferably, in anotherembodiment, the oil composition of section I has been partiallyhydrogenated and has a content of less than about 0.1, 0.2, 0.3, 0.4,0.5, 0.6, 0.7, 0.8, 0.9 or 1 wt. % trans-fatty acids based on a totalweight of fatty acids or derivatives thereof in the composition.

For any one of the preceding oil compositions described above, thecomposition can include less than about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6,0.7, 0.8, 0.9, 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0 or 10 wt. %saturated fatty acid or a derivative thereof. Oils low in saturated fatare often preferred by consumers for the health benefits attributed tothem as compared to oils that are relatively high in saturated fatcontent. In one embodiment, such oils are derived from geneticallymodified plant oils containing decreased levels of saturated fats.Examples include seeds of plants derived from palm, coconut, peanut,cottonseed, corn, maize, flax, canola, rapeseed, linseed, flax, soybean,canola, rapeseed, safflower, sunflower and mixtures thereof. Exemplarysaturated fats include myristic acid (C14:0), palmitic acid (C16:0) andstearic acid (C18:0).

For any one of the oil compositions described above and containing lessthan 8 wt. % α-linolenic acid or a derivative thereof, the compositionhas a significantly better flavor quality as compared to that of an oilcomprising about 8-10 wt. % α-linolenic acid or a derivative thereof andotherwise having the same composition, wherein flavor quality isdetermined by a standardized sensory evaluation. Further, for any one ofthe oil compositions described and containing less than 8 wt. %α-linolenic acid or a derivative thereof, the composition has asignificantly decreased room-odor intensity as compared to that of anoil comprising about 8-10 wt. % α-linolenic acid or a derivative thereofand otherwise having the same composition, a significant difference inoverall room-odor intensity being indicated by a difference of greaterthan 1.0 obtained in a standardized sensory evaluation.

For any one of the oil compositions described above, the composition ofthe crude oil is such that it can have a peroxide value of 0 meq/kg.

For any one of the preceding oil compositions described above, thecomposition is storage stable under refrigeration for at least 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22,23, or 24 months or more.

For any one of the preceding oil compositions described above in sectionI., the composition is storage stable at about room temperature for atleast 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19,20, 21, 22, 23, or 24 months or more.

For any one of the preceding oil compositions described above in sectionI., the composition is storage stable at a temperature of from 5 toabout 45° C. for at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,15, 16, 17, 18, 19, 20, 21, 22, 23, or 24 months or more.

For any one of the preceding oil compositions described above, theanisidine value can be not more than about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6,0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0,2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9 or 3.0.

For any one of the preceding oil compositions described above, theperoxide value can be not more than 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7,0.8, 0.9 or 1.0 meq/kg.

For any one of the preceding oil compositions described above,composition can comprise not more than about 0.1, 0.2, 0.3, 0.4, 0.5,0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9,2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9 or 3.0 wt. %α-linolenic acid or a derivative thereof.

For any one of the preceding oil compositions described above,composition can comprise not more than 5, 10, 15, 20, 25, 30, 35, 40,45, 50 or 55 wt. % linoleic acid or a derivative thereof.

In a further embodiment, an oil composition described above has asignificantly reduced overall room-odor intensity relative to theoverall room-odor intensity of an oil having an anisidine value greaterthan about 2.0, wherein the room-odor intensity is determined by astandardized sensory evaluation as described above.

In another embodiment, any of the preceding oil compositions describedabove can be blended oil compositions. The oil compositions can resultfrom blending of the whole seeds, blending of the seed meats, flakes,fines, miscella, crude oil, refined oil, refined and bleached oil orrefined, bleached and deodorized oil. Blending or interesterification oflow ALA oil compositions with high SDA oil compositions, high stearicoil compositions, corn oil compositions, partially hydrogenated oilcompositions, wheat germ oil compositions, and canola oil compositions,for example, enhance stability, quality and functionality of the oilcompositions, particularly for use in foods or for frying. The oilcompositions of the invention can also be a blend of a marine oil madewith a process of the invention and a plant oil made with a process ofthe invention; marine oil made with a process of the invention and aplant oil; an oil containing at least one polyunsaturated fatty acidhaving four or more carbon-carbon double bonds or a derivative thereofmade with a process of the invention and a plant oil made with a processof the invention; an oil containing at least one polyunsaturated fattyacid having four or more carbon-carbon double bonds or a derivativethereof made with a process of the invention and a plant oil; or an oilcontaining at least one polyunsaturated fatty acid having four or morecarbon-carbon double bonds or a derivative thereof and a plant oil madewith a process of the invention.

Along with enhancement of the oxidative stability of the oilcompositions without added stabilizing compounds, the oil compositionscan further include stabilizers. Stabilizers, generally, are added tothe oil compositions to lengthen the initiation phase and delay theonset of the propagation phase. Stabilizers can delay the onset of thepropagation phase by up to about 15 times or more as compared to thetime to the propagation phase in an oil having no added stabilizers.Depending on the identity of the particular stabilizer, these compoundscan have different modes of action. Some stabilizers chelate metals orother catalytic species that would otherwise interact with thetriglycerides of the oil and increase the rate of oxidation of the oil.Other stabilizers act as antioxidant molecules and react with freeradical species which could oxidize the fatty acids of the triglyceridesto peroxides, which can in turn oxidize with other fatty acids asdescribed in more detail above in section I.A.

Exemplary stabilizers can include anoxomer, ascorbic acid, ascorbylpalmitate, ascorbyl stearate, butylated hydroxyanisole (BHA), butylatedhydroxytoluene (BHT), t-butyl hydroquinone (TBHQ),3-t-butyl-4-hydroxyanisole, calcium ascorbate, calcium disodium EDTA,catalase, cetyl gallate, citric acid, clove extract, coffee beanextract, 2,6-di-t-butylphenol, dilauryl thiodipropionate, disodiumcitrate, disodium EDTA, dodecyl gallate, edetic acid, erythorbic acid,6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, ethyl gallate, ethylmaltol, eucalyptus extract, fumaric acid, gentian extract, glucoseoxidase, heptyl paraben, hesperetin,4-hydroxymethyl-2,6-di-t-butylphenol, N-hydroxysuccinic acid, isopropylcitrate, lecithin, lemon juice, lemon juice solids, maltol, methylgallate, methylparaben, octyl gallate, phosphatidylcholine, phosphoricacid, pimento extract, potassium bisulfite, potassium lactate, potassiummetabisulfite, potassium sodium tartrate anhydrous, propyl gallate, ricebran extract, rosemary extract, sage extract, sodium ascorbate, sodiumerythorbate, sodium hypophosphate, sodium ascorbate, sodium erythorbate,sodium hypophosphate, sodium metabisulfite, sodium sulfite, sodiumthisulfate pentahydrate, soy flour, sucrose, L-tartaric acid,α-terpineol, tocopherol, D-α-tocopherol, DL-α-tocopherol, tocopherylacetate, D-α-tocopheryl acetate, DL-α-tocopheryl acetate,2,4,5-trihydroxybutyrophenone, wheat germ oil, and combinations thereof.

II. Process for Preparing Oil Compositions

Generally, the following steps are used to process seed oils:preparation, cracking and dehulling, conditioning, milling, flaking orpressing, extracting, degumming, refining, bleaching and deodorizing.Each of these steps will be discussed in more detail herein below. Thediscussion details the process for each of the steps used currently incommercial application. A person of ordinary skill would know that thesteps could be combined, used in a different order or otherwisemodified.

Generally, the preparation step includes the initial cleaning process,which removes stones, dirt, sticks, worms, insects, metal fragments, andother debris collected during the harvest and storage of the seeds.Extraneous matter as described above can affect the quality of the finalseed oil by containing compounds that negatively impact its chemicalstability. Preferably, ripe, unbroken seeds having reduced levels ofchlorophyll and reduced levels of free fatty acids are used.

After the preparation step, the seeds are cracked and dehulled. Crackingand dehulling can be accomplished in a variety of ways, which are wellknown in the art. For example, the seeds can be cracked and dehulledusing a seed cracker, which mechanically breaks the seeds and releaseshulls and directly exposes the inner seed meat to air. After cracking,the hulls can be separated from the seed meats by a dehuller. In oneaspect, the dehuller can separate the hulls from the seed meats due tothe density difference between the hulls and the seeds; the hulls areless dense than the seed meats. For example, aspiration will separatethe hulls from the cracked seed meats. Dehulling reduces the crude fibercontent, while increasing the protein concentration of the extractedseed meats. Optionally, after dehulling, the hulls can be sieved torecover the fines generated in the cracking of the seeds. Afterrecovery, the fines can be added back to the seed meats prior toconditioning.

Once the seeds are cracked, the oxygen exposure of the seed meats canoptionally be minimized, which would reduce oil oxidation and improveoil quality. Furthermore, it will be understood by persons skilled inthe art that minimization of oxygen exposure may occur independently ateach of the subsequently disclosed oilseed processing steps.

Once the seeds are cracked and dehulled, they are conditioned to makethe seed meats pliable prior to further processing. Furthermore, theconditioning ruptures oil bodies. Further processing, in terms offlaking, grinding or other milling technology is made easier by havingpliable seed meats at this stage. Generally, the seed meats havemoisture removed or added in order to reach a 6-10 wt. % moisture level.If moisture is removed, this process is called toasting and if moistureis added, this process is called cooking. Typically, the seed meats areheated to 40-90° C. with steam which is dry or wet depending on thedirection of adjustment of the moisture content of the seed meats. Insome instances, the conditioning step occurs under conditions minimizingoxygen exposure or at lower temperatures for seeds having high PUFAlevels.

Once the seed meats are conditioned, they can be milled to a desiredparticle size or flaked to a desired surface area. In certain cases, theflaking or milling occurs under conditions minimizing oxygen exposure.Flaking or milling is done to increase the surface area of the seedmeats and also rupture the oil bodies thereby facilitating a moreefficient extraction. Many milling technologies are appropriate and arewell known in the art. The considerations when choosing a method ofmilling and a particle size for the ground seed are contingent upon, butnot limited to the oil content in the seed and the desired efficiency ofthe extraction of the seed meats or the seed. When flaking the seedmeats, the flakes are typically from about 0.1 to about 0.5 mm thick;from about 0.1 to about 0.35 mm thick; from about 0.3 to about 0.5 mmthick; or from about 0.2 to about 0.4 mm thick.

Optionally, after the seed meats are milled, they can be pressed.Typically, the seed meats are pressed when the oil content of the seedmeats is greater than about 30 wt. % of the seeds. However, seeds withhigher or lower oil contents can be pressed. The seed meats can bepressed, for example, in a hydraulic press or mechanical screw.Typically, the seed meats are heated to less than about 55° C. upon theinput of work. When pressed, the oil in the seed meats is pressedthrough a screen, collected and filtered. The oil collected is the firstpress oil. The seed meats from after pressing are called seed cake; theseed cake contains oil and can be subjected to solvent extraction.

After milling, flaking or optional pressing, the oil can be extractedfrom the seed meats or seed cake by contacting them with a solvent.Preferably, n-hexane or iso-hexane is used as the solvent in theextraction process. Typically, the solvent is degassed prior to contactwith the oil. This extraction can be carded out in a variety of ways,which are well known in the art. For example, the extraction can be abatch or continuous process and desirably is a continuouscounter-current process. In a continuous counter-current process, thesolvent contact with the seed meat leaches the oil into the solvent,providing increasingly more concentrated miscellas (i.e., solvent-oil),while the marc (i.e., solvent-solids) is contacted with miscellas ofdecreasing concentration. After extraction, the solvent is removed fromthe miscella in a manner well known in the art. For example,distillation, rotary evaporation or a rising film evaporator and steamstripper can be used for removing the solvent. After solvent removal, ifthe crude oil still contains residual solvent, it can be heated at about95° C. and about 60 mmHg.

The above processed crude oil contains hydratable and nonhydratablephosphatides. Accordingly, the crude oil is degummed to remove thehydratable phosphatides by adding water and heating to from about 40 toabout 75° C. for approximately 5-60 minutes depending on the phosphatideconcentration. Optionally, phosphoric acid and/or citric acid can beadded to convert the nonhydratable phosphatides to hydratablephosphatides. Phosphoric acid and citric acid form metal complexes,which decreases the concentration of metal ions bound to phosphatides(metal complexed phosphatides are nonhydratable) and thus, convertsnonhydratable phosphatides to hydratable phosphatides. Optionally, afterheating with water, the crude oil and water mixture can be centrifugedto separate the oil and water, followed by removal of the water layercontaining the hydratable phosphatides. Generally, if phosphoric acidand/or citric acid are added in the degumming step, about 1 wt. % toabout 5 wt. %; preferably, about 1 wt. % to about 2 wt. %; morepreferably, about 1.5 wt. % to about 2 wt. % are used. This process stepis optionally carried out by degassing the water and phosphoric acidbefore contacting them with the oil.

Furthermore, the crude oil contains free fatty acids (FFAs), which canbe removed by a chemical (e.g., caustic) refining step. When FFAs reactwith basic substances (e.g., caustic) they form soaps that can beextracted into aqueous solution. Thus, the crude oil is heated to about40 to abou 75° C. and NaOH is added with stirring and allowed to reactfor approximately 10 to 45 minutes. This is followed by stopping thestirring while continuing heat, removing the aqueous layer, and treatingthe neutralized oil to remove soaps. The oil is treated by water washingthe oil until the aqueous layer is of neutral pH, or by treating theneutralized oil with a silica or ion exchange material. The oil is driedat about 95° C. and about 10 mmHg. In some instances, the causticsolution is degassed before it contacts the oil.

Alternatively, rather than removing FFAs from the oil by chemicalrefining, the FFAs can be removed by physical refining. For example, theoil can be physically refined during deodorization. When physicalrefining is performed, the FFAs are removed from the oil by vacuumdistillation performed at low pressure and relatively highertemperature. Generally, FFAs have lower molecular weights thantriglycerides and thus, FFAs generally have lower boiling points and canbe separated from triglycerides based on this boiling point differenceand through aid of nitrogen or steam stripping used as an azeotrope orcarrier gas to sweep volatiles from the deodorizers.

Typically, when physical refining rather than chemical refining isperformed, oil processing conditions are modified to achieve similarfinal product specifications. For example, when an aqueous acidicsolution is used in the degumming step, a higher concentration of acid(e.g., up to about 100% greater concentration, preferably about 50% toabout 100% greater concentration) may be needed due to the greaterconcentration of non-hydratable phosphatides that could otherwise beremoved in a chemical refining step. In addition, a greater amount ofbleaching material (e.g., up to about 100% greater amount, preferablyabout 50 to about 100% greater amount) is used.

Before bleaching citric acid (50 wt. % solution) can be added at aconcentration of about 0.01 wt. % to about 5 wt. % to the degummed oiland/or chemically refined oil. This mixture can then be heated at atemperature of about 35° C. to about 65° C. and a pressure of about 1mmHg to about 760 mmHg for about 5 to about 60 minutes.

The degummed oil and/or chemically refined oil is subjected to anabsorption process (e.g., bleached) to remove peroxides, oxidationproducts, phosphatides, keratinoids, chlorphyloids, color bodies, metalsand remaining soaps formed in the caustic refining step or otherprocessing steps. The bleaching process comprises heating the degummedoil or chemically refined oil under vacuum of about 0.1 mmHg to about200 mmHg and adding a bleaching material appropriate to remove the abovereferenced species (e.g., neutral earth (commonly termed natural clay orfuller's earth), acid-activated earth, activated clays and silicates)and a filter aid, whereupon the mixture is heated to about 75-125° C.and the bleaching material is contacted with the degummed oil and/orchemically refined oil for about 5-50 minutes. It can be advantageous todegas the bleaching material before it contacts the refined oil. Theamount of bleaching material used is from about 0.25 wt. % to about 3wt. %, preferably about 0.25 wt. % to about 1.5 wt. %, and morepreferably about 0.5 wt. % to about 1 wt. %. After heating, the bleachedoil or refined, bleached oil is filtered and deodorized.

The bleached oil or refined, bleached oil is deodorized to removecompounds with strong odors and flavors as well as remaining free fattyacids. The color of the oil can be further reduced by heat bleaching atelevated temperatures. Deodorization can be performed by a variety oftechniques including batch and continuous deodorization units such asbatch stir tank reactors, falling film evaporators, wiped filmevaporators, packed column deodorizers, tray type deodorizers, and loopreactors. Typically, a continuous deodorization process is preferred.Generally, deodorization conditions are performed at about 160 to about270° C. and about 0.002 to about 1.4 kPa. For a continuous process,particularly in a continuous deodorizer having successive trays for theoil to traverse, a residence time of up to 2 hours at a temperature fromabout 170° C. to about 265° C.; a residence time of up to about 30minutes at a temperature from about 240° C. to about 250° C. ispreferred. Deodorization conditions can use carrier gases for theremoval of volatile compounds (e.g., steam, nitrogen, argon, or anyother gas that does not decrease the stability or quality of the oil).

Furthermore, when physical rather than chemical refining is used, agreater amount of FFAs are removed during the deodorization step, andthe deodorizer conditions are modified to facilitate the removal of freefatty acids. For example, the temperature is increased by about 25° C.;oils can be deodorized at temperatures ranging from about 165° C. toabout 300° C. In particular, oils can be deodorized at temperaturesranging from about 250° C. to about 280° C. or about 175° C. to about205° C. In addition, the retention time of the oil in the deodorizer isincreased by up to about 100%. For example, the retention time can rangefrom less than about 1, 5, 10, 30, 60, 90, 100, 110, 120, 130, 150, 180,210 or 240 minutes. Additionally, the deodorizer pressure can be reducedto less than about 3×10⁻⁴, 1×10⁻³, 5×10⁻³, 0.01, 0.02, 0.03, 0.04, 0.05,0.06, 0.07, 0.08, 0.09, or 0.1 kPa. The deodorization step results in arefined, bleached and deodorized (RBD) oil.

Optionally, RBD oils can be stabilized by partial hydrogenation and/orby the addition of stabilizers or by minimizing the removal ordegradation of microcomponents that aid in maintaining oil stability andquality. Partial hydrogenation stabilizes an oil by reducing the numberof double bonds in the fatty acids contained in the oil and thus,reducing the chemical reactivity of the oil. However, partialhydrogenation can increase the concentration of undesirable trans-fattyacids.

Stabilizers generally act to intercept free radicals formed duringoxidation. Interception of the free radicals by stabilizers, whichbecome either more stable free radicals or rearrange to become stablemolecules, slows the oxidation of the oil due to the decreasedconcentration of highly reactive free radicals that can oxidize morefatty acid units.

For each of the above steps in section II., at each step the exposure tooxygen was optionally minimized, the exposure to heat was optionallyminimized, the exposure to UV light was optionally minimized andoptionally, stabilizers were added to the seed meats or seed oil before,during, or after processing. These and other process improvements forpreparing oils of the present invention are described and exemplified inU.S. patent application Ser. No. ______ entitled “Processes forPreparation of Oil Compositions” filed Nov. 4, 2005, attorney docket no.MTC 6921.201 (38-21(53354C)), which is incorporated by reference hereinin its entirety.

III. Handling and Storage of Oil Compositions

Generally, when storing oil compositions it is advantageous to minimizefurther oxidation of the fatty acids. One way to do this is to store theoils in the dark or in substantially opaque containers, keep them at amoderate temperature and preferably, in the presence of an inert gas.Preferably, the oil has stability characteristics, which paired withstorage conditions and/or stabilizers, will inhibit the reversion of theoil's flavor, odor, color, and the like.

Oil compositions described above in section I. typically haveadvantageous storage stability characteristics.

For example, in one embodiment, a process for maintaining the storagestability of an oil during shipment or storage comprises storing an oildescribed in section I. in a container at a temperature ranging fromabout 4 to about 45° C. for at least one month, wherein the oil has ananisidine value of less than 3 after storage. In another embodiment, aprocess for maintaining the storage stability of an oil during shipmentor storage comprises storing an oil of the invention in a container at atemperature ranging from about 4 to about 45° C. for at least one month,wherein the absolute change in the anisidine value of the oil duringstorage is no more than about 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7,0.8, 0.9, 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10, 11, 12, 13,14, 15, 16, 17, 18, 19 or 20. Further, the oil can be stored in anoxygen-free or reduced-oxygen atmosphere. Preferably, the oil can bestored at about room temperature; preferably, the oil can be stored atabout room temperature for about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12months or more. Alternatively, the oil can be stored under refrigerationfor at least one month; further, the oil can be stored underrefrigeration for about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 months ormore. In another embodiment, the oil is derived from a source other thana marine oil, such as fish, algae, or krill. In a further embodiment ofthe process of this section, the oil is derived from a plant oil otherthan blackcurrant oil, borage oil, Echium oil, evening primrose oil,gooseberry oil, hemp oil, or redcurrant oil.

The process described above in section III. can further compriseaddition of a stabilizer to the oil prior to or during storage. Thestabilizer can comprise at least one complexing agent or at least oneantioxidant. In one exemplary embodiment, the stabilizer comprisescitric acid, TBHQ, ascorbyl palmitate, propyl gallate, or derivatives orcombinations thereof.

IV. Food Products

Food products can be prepared comprising anyone of the oil compositionsdescribed above in section I. In one embodiment, the food product orfood analog has a significantly better flavor quality as compared tothat of the same food product or food analog fried in a soy oilcomprising about 8-10 wt. % α-linolenic acid or a derivative thereof,wherein flavor quality is determined by a standardized sensoryevaluation. In another embodiment, the oil has significantly decreasedoverall room-odor intensity as compared to that of a soy oil comprisingabout 8-10 wt. % α-linolenic acid or a derivative thereof, a significantdifference in overall room-odor intensity being indicated by adifference of greater than 1.0 obtained in a standardized sensoryevaluation.

Another aspect of the present invention is a method of making a foodcomposition comprising frying a food product or food analog in an oilcomposition described above in sections I.A. through I.D. Further, themethod produces the food product or food analog has a significantlybetter flavor quality as compared to that of the same food product orfood analog fried in an oil comprising about 8-10 wt. % α-linolenic acidor a derivative thereof and otherwise having the same composition,wherein flavor quality is determined by a standardized sensoryevaluation. Advantageously, the oil used in the method of frying hassignificantly decreased overall room-odor intensity as compared to thatof an oil comprising about 8-10 wt. % α-linolenic acid or a derivativethereof and otherwise having the same composition, a significantdifference in overall room-odor intensity being indicated by adifference of greater than 1.0 obtained in a standardized sensoryevaluation.

In another embodiment, the method of frying uses an oil having a fryinglife at least 25% longer as compared to that of an oil comprising about8-10 wt. % α-linolenic acid or a derivative thereof and otherwise havingthe same composition.

Having described the invention in detail, it will be apparent thatmodifications and variations are possible without departing the scope ofthe invention defined in the appended claims. Furthermore, it should beappreciated that all examples in the present disclosure are provided asnon-limiting examples.

EXAMPLES Example 1 Sensory Evaluation of Low ALA Oil

Oils as processed using the process described above in section I. wereevaluated in a frying application using tortilla chips as the endproduct for evaluation. Tortilla chips were selected based upon theirpopularity in the marketplace, ease of test execution relative to potatochips, and their high oil absorption rate. Oils were compared to threecommercially available frying oil options (one corn, two soy). Tortillachips and oil were collected at frequent intervals throughout a 24 hourfrying period. Analytical and sensory tests were conducted on thesamples. Summarized below are the findings of the sensory analysis forthe oils and the tortilla chips that received no shelf life age.

Sensory Findings

-   Sensory panelists were able to detect differences between samples.-   Frying oil order changed with frying time but remained within    acceptable ranges for all oils tested.-   Tortilla chip attributes did not change appreciably as a function of    frying time.-   Tortilla chip attributes were within acceptable ranges for most of    the key attributes across all oils.-   When differences existed, the low ALA oils were better than the    commercial soy oil included in the test.    Detailed Description of Findings

Part 1. Materials

Two low ALA oil samples, differing only in the presence or absence of anantioxidant were tested. Three different commercially available fryingoils from ADM were selected for the study. An industry standard corn oilwas chosen for inclusion based upon its heavy usage in tortilla chipfrying applications. A soybean oil stated to be appropriate for lightfrying applications with high turnover rates was selected as a directcomparison to the experimental options. The third commercial oil was apartially hydrogenated soy oil with high resistance to breakdown,intended for extended frying life. The coding system used throughout allof this report is PHS=partially hydrogenated soy, LLSY=low ALA soy withantioxidant and LLSN=low ALA soy without antioxidant.

Tortilla chips for the study were hand cut from six-inch white corntortillas supplied by Azteca Foods, Inc. Thickness of the tortillas was1.17-1.24 mm. Products were cut into triangles using a template. Sizewas designed so that the cumulative weight of five chips would achievethe desired fryer load. The tortillas were less than one week of agewhen cut into chips. Chips were held at 0° F. until the time of thestudy. Frozen chips were removed from storage and thawed at roomtemperature 12-18 hours prior to use.

Presto brand Fry Daddy fryers (model 05420) were used for the study.Each fryer was equipped with an external temperature controller fromJ-Kem. A separate fryer was dedicated to each oil variable for theduration of the study.

A tortilla chip industry standard film for packaging samples wasobtained from Printpack, Inc. HDPE bottles were used for oil samplessent for analytical testing. Glass vials were used for oil samplescollected for sensory order testing.

Part 2. Protocol

Fryers were loaded with 965 g of oil at the outset of the study, whichwas the amount required to reach the internally marked fill line. Fryerswere allowed to preheat for 30 minutes prior to the start of frying eachday. Fryer load ratio (chip weight to oil weight) was based uponcommercial frying operational data. Frying conditions were 180° C. forone minute. Temperature readings from the controllers were recordedevery 15 minutes on day one of frying and then hourly on subsequentdays.

At the end of each frying cycle of one minute, chip samples wereremoved. Ten seconds after chip removal, another load was added to thefryer in an attempt to simulate continuous frying conditions as closelyas possible while using a batch process. Chips were removed anddiscarded except for the selected collection time periods. Oil was addedto the fryers every hour to restore the level to the original fill line.

Both chips and oil were collected at time zero and then every threehours over a twenty-four hour frying period. Tortilla chip samples werecollected the last five minutes of each three hour frying period.Samples were removed from the oil, then placed in a single layer on abakery cooling rack so that excess oil could drain from the product.Samples were placed into film packages and then put in frozen storageuntil the time of sensory evaluation. After frying for three hours, oilwas allowed to cool and was then filtered through a paper coffee filterto remove fragments of chips. After filtration, samples of oil werecollected for analytical and sensory testing. Filtered oil was returnedto the fryer. Oil level was restored to the fill line with fresh oil.Once the process was complete and the fryers returned to temperature,the study resumed. Chips were fried for a total of six hours per dayover the course of four days. Total amount of oil consumed for the studywas tracked on a cumulative basis and not at each hourly addition.Amount lost during filtration was not individually tracked but assumedto be constant across all variables and was included as part of thetotal.

It should be noted that one oil sample was compromised during thecollection period. Fresh oil was added to the LLSY fryer prior to thecollection of the 24 hour sample. The impact would be limited toanalytical and sensory analysis of the oil.

Oil samples were submitted for analytical testing. Small vials of oilwere retained for sensory order testing. Sensory testing was also usedfor the evaluation of the tortilla chips.

Products were evaluated by five or six panelists. Selection ofattributes to include in the evaluation, appropriate terminology and theapproach were developed by the sensory panel. Sixty point linear scaleswere selected for use on all attributes. A separate training session wasconducted on the oils and the chips prior to the execution of the tests.Labeled reference products were provided as part of the training sessionand were included in the testing itself.

Sensory data from the testing was analyzed using ANOVA followed bypaired comparison testing using Duncan's methodology. Data were notblocked by panelist for the analysis. Samples within a given collectiontime period were compared to one another to determine whether there wereany statistically significant differences between the products.

Sensory attribute means were compiled for each variable at everycollection time period. Those means were then plotted as a function offrying time for each sensory attribute to determine whether sensoryattributes were changing. No statistical analysis was conducted on themeans as a function of frying time.

Part 3. Discussion of Findings

Sensory Analysis of Oils

The total oil odor intensity and the off odor intensity were measured onthe oil samples. The overall oil odor intensity was within theacceptance range for all oils at all collection periods. Within anygiven sampling time (frying oil age), differences between oil types weresmall and not statistically significant. Intensity of oil odor increasedbetween time zero and six hours with the greatest change occurringbetween zero and three hours. Intensity reached a plateau between sixand nine hours for all oils except partially hydrogenated soy which wasbetween nine and twelve hours of frying.

Off odor intensity levels were within the acceptance range for all oilsat all times with one exception. Partially hydrogenated soy slightlyexceeded the acceptance limit at 12 hours of frying. As with the oilintensity, the differences between oils within a time period was smalland not statistically significant. There was one exception and that wasthat partially hydrogenated soy oil had a higher off odor intensity thanlow ALA soy without antioxidant at the 12 hour sampling period. Off odorintensity increased and reached a plateau in the very same manner as theoverall oil odor intensity.

Sensory Analysis on Tortilla Chips

Ten different attributes were measured on the tortilla chips. Time zerowas measured as a point of reference only for the changes that occurredas a function of frying time. In commercial practice, time zero wouldnever exist; therefore, the discussion of sensory findings will excludetime zero unless otherwise noted. Sensory crispness was dropped from theanalysis because the panelists did not find differences between sampleswithin or between sampling periods. This left a total of nine attributesmeasured over the period of 3-24 hours of frying time.

Six of the nine attributes were within their respective acceptanceranges for all oils at all time periods. Those attributes were color,color uniformity, oil flavor intensity, oil coat in the mouth, offflavor intensity and overall acceptability. For three of the attributes,selected oils were out of the acceptance ranges for one or more of thetime periods. The attribute with the most oils and frequency of productsout of the acceptable range was oil intensity. Corn flavor intensity wastoo low in selected instances.

Oil Types Out of Acceptance Ranges Frying Time Tactile Oil Odor CornFlavor (hrs) Oiliness Intensity Intensity 3 Soy Soy PHS 6 Soy Soy PHSCorn 9 Soy 12 Soy Soy PHS PHS 15 Soy Soy PHS LLSY LLSN 18 Soy Soy SoyCorn PHS PHS LLSY Corn LLSY 21 Soy PHS 24

Whether the attributes were within or outside of their respectiveacceptance ranges, statistically significant differences existed. Whenthe differences existed, the low ALA oils usually performed better thansoy and partially hydrogenated soy oils. Performance of the low ALA oilswas closest to the corn oil.

When using 60 point linear scales, breakpoints in the data were used toestablish how meaningful the differences may be. A difference of 6-10points is considered to be clear, but not large. It is a magnitude thatmay be detected by a panel trained for the product's evaluation and byindividuals familiar with the product line. A difference greater than 10points is generally large enough for a consumer to notice. The tablebelow summarizes the differences between oils that were 10 points orgreater and were statistically significant at the 90 or 95% confidencelevel. This summary is to demonstrate how the low ALA oils performedrelative to the commercial oils, bearing in mind that the comparisonsmay be drawn on samples that were all within their respective acceptablelimits.

Statistically Significant Differences>10 Points Frying Time Attribute(hrs) Direction and Magnitude Oil Odor Intensity 18 LLSN < Soy (10 pts)Oil Flavor Intensity 3 LLSY < Soy (11 pts) 12 LLSY < Soy (10 pts) 18LLSN < Soy (12 pts) 18 Corn < Soy (10 pts) Off Flavor Intensity 6 LLSY,LLSN, CORN < Soy (11-12 pts) 9 Corn < Soy (10 pts) 12 LLSY, LLSN, Corn <Soy (12-13 pts) 15 Corn < Soy (10 pts) 18 Corn, LLSN < Soy (11-12 pts)Overall Acceptability 3 LLSN > Soy (10 pts) 6 LLSY > Soy (10 pts) 18Corn > Soy (12 pts)

Sensory means for each of the tortilla chip attributes were plotted as afunction of frying time. The pattern of change in intensity followed bya plateau noted when testing the frying oils was not repeated in thetortilla chips. Most of the values for the attributes remained unchangedas a function of frying time. The panelists could detect a change in theoils but those changes were not evident in the tortilla chips fried inthe oils.

Graphs of certain sensory attributes of the oils versus the frying timeage of the oils are depicted in FIG. 1-3.

1-68. (canceled)
 69. An oil composition comprising linoleic acid or a derivative thereof, and less than about 3 wt. % α-linolenic acid or a derivative thereof, based upon the total weight of fatty acids or derivatives thereof in the composition, and either: (a) the composition having an anisidine value of less than 2, the composition being derived from a non-algal plant oil and being unhydrogenated; (b) the composition having an anisidine value of less than 2, and being derived from soy; (c) the composition having a peroxide value of less than 0.3 meq/kg when the composition is free of added stabilizers, and being derived from soy; (d) the composition having a peroxide value of 0 meq/kg, and being a crude soy oil; (e) less than 1 wt. % trans-fatty acid based upon the total weight of fatty acids or derivatives thereof in the composition, and being derived from soy; (f) comprising less than 56.0 wt. % linoleic acid, and being derived from soy; or (g) not more than about 80 wt. % oleic acid or a derivative thereof, based upon the total weight of fatty acids or derivatives thereof in the composition, and at least 800 ppm tocopherols, and the composition being derived from soy.
 70. The composition of claim 69 wherein the composition is derived from almond, avocado, babassu, borage, blackcurrant seed, canola, castor bean, coconut, corn, cottonseed, Echium, evening primrose, flax seed, gooseberry, grapeseed, groundnut, hazelnut, linseed, mustard, olive, palm, palm kernel, peanut, perilla, pine seed, poppy seed, pumpkin seed, rapeseed, redcurrant, rice bran, safflower, sesame seed, soybean, sunflower, tea, walnut, or wheat germ oil.
 71. The composition of claim 69 wherein the composition is derived from an oil other than a marine oil.
 72. The composition of claim 69 wherein the composition comprises at least 850 ppm tocopherols.
 73. The composition of claim 69 wherein the anisidine value is not more than
 1. 74. The composition of claim 69 wherein the oil composition has a frying life at least 25% longer as compared to that of a reference oil composition comprising about 8-10 wt. % α-linolenic acid or a derivative thereof and otherwise having the same composition except that the linoleic acid content of the reference oil composition is decreased such that the sum of linoleic acid and α-linolenic acid within both compositions is equivalent.
 75. A soy oil composition comprising not more than about 8 wt. % α-linolenic acid or a derivative, based upon the total weight of fatty acids or derivatives thereof in the composition, and either: (a) from about 55 to about 85 wt. % oleic acid or a derivative thereof, and from about 2 to about 35 wt. % linoleic acid or a derivative thereof; (b) from about 25 to about 85 wt. % oleic acid or a derivative thereof, from about 2 to about 65 wt. % linoleic acid or a derivative thereof, and not more than about 10 wt. % saturated fatty acid or a derivative thereof; or (c) from about 20 to about 30 wt. % stearic acid or a derivative thereof, not more than about 40 wt. % linoleic acid or a derivative thereof, not more than about 30 wt. % oleic acid or a derivative thereof, and not more than about 10 wt. % palmitic acid or a derivative thereof.
 76. The composition of claim 69 comprising not more than about 10 wt. % saturated fatty acid or a derivative thereof.
 77. The composition of claim 75 comprising not more than about 10 wt. % palmitic acid or a derivative thereof.
 78. The composition of claim 75 comprising not more than about 8 wt. % α-linolenic acid or a derivative thereof.
 79. The composition of claim 69 wherein the composition is storage stable at about room temperature for at least one month.
 80. The composition of claim 69 wherein the composition is storage stable at a temperature of from 5 to about 45° C. for at least one month.
 81. The composition of claim 69 wherein the composition is derived from a plant oil other than blackcurrant oil, borage oil, Echium oil, evening primrose oil, gooseberry oil, hemp oil, or redcurrant oil.
 82. The composition of claim 69 wherein the composition comprises from about 2.2 to about 2.8 wt. % α-linolenic acid or a derivative thereof.
 83. The composition of claim 69 wherein the composition has a significantly better flavor quality as compared to that of a reference oil comprising about 8-10 wt. % α-linolenic acid or a derivative thereof and otherwise having the same composition except that the linoleic acid content of the reference oil composition is decreased such that the sum of linoleic acid and α-linolenic acid within both compositions is equivalent, wherein flavor quality is determined by a standardized sensory evaluation.
 84. The composition of claim 69 wherein the composition has significantly decreased overall room-odor intensity as compared to that of a reference oil comprising about 8-10 wt. % α-linolenic acid or a derivative thereof and otherwise having the same composition except that the linoleic acid content of the reference oil composition is decreased such that the sum of linoleic acid and α-linolenic acid within both compositions is equivalent, a significant difference in overall room-odor intensity being indicated by a difference of greater than 1.0 obtained in a standardized sensory evaluation.
 85. A food, beverage, nutritional supplement, or cooking oil comprising the oil of claim
 69. 86. A method of making a food composition, said method comprising frying a food product or food analog in an oil of claim
 69. 87. The method of claim 86 wherein the food product or food analog has a significantly better flavor quality as compared to that of the same food product or food analog fried in a reference oil comprising about 8-10 wt. % α-linolenic acid or a derivative thereof and otherwise having the same composition except that the linoleic acid content of the reference oil composition is decreased such that the sum of linoleic acid and α-linolenic acid within both compositions is equivalent, wherein flavor quality is determined by a standardized sensory evaluation.
 88. The method of claim 86 wherein the oil has significantly decreased overall room-odor intensity as compared to that of a reference oil comprising about 8-10 wt. % α-linolenic acid or a derivative thereof and otherwise having the same composition except that the linoleic acid content of the reference oil composition is decreased such that the sum of linoleic acid and α-linolenic acid within both compositions is equivalent, a significant difference in overall room-odor intensity being indicated by a difference of greater than 1.0 obtained in a standardized sensory evaluation. 